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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
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  • C01—INORGANIC CHEMISTRY
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  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
  • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
  • C01B33/44—Products obtained from layered base-exchange silicates by ion-exchange with organic compounds such as ammonium, phosphonium or sulfonium compounds or by intercalation of organic compounds, e.g. organoclay material
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/0066—Use of inorganic compounding ingredients
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  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/06—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent
  • C08J9/10—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a chemical blowing agent developing nitrogen, the blowing agent being a compound containing a nitrogen-to-nitrogen bond
  • C08J9/102—Azo-compounds
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  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
  • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
  • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
  • C08J9/122—Hydrogen, oxygen, CO2, nitrogen or noble gases
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/04—Polyesters derived from hydroxycarboxylic acids, e.g. lactones
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G2261/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
  • C08G2261/10—Definition of the polymer structure
  • C08G2261/12—Copolymers
  • C08G2261/126—Copolymers block
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  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
  • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
  • C08G63/68—Polyesters containing atoms other than carbon, hydrogen and oxygen
  • C08G63/695—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon
  • C08G63/6952—Polyesters containing atoms other than carbon, hydrogen and oxygen containing silicon derived from hydroxycarboxylic acids
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2203/00—Foams characterized by the expanding agent
  • C08J2203/08—Supercritical fluid
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
  • C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K3/00—Use of inorganic substances as compounding ingredients
  • C08K3/34—Silicon-containing compounds
  • C08K3/346—Clay
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
  • C08K5/0033—Additives activating the degradation of the macromolecular compound
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K5/00—Use of organic ingredients
  • C08K5/16—Nitrogen-containing compounds
  • C08K5/17—Amines; Quaternary ammonium compounds
  • C08K5/19—Quaternary ammonium compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
  • C08K9/00—Use of pretreated ingredients
  • C08K9/04—Ingredients treated with organic substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L83/00—Compositions of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen or carbon only; Compositions of derivatives of such polymers
  • C08L83/10—Block- or graft-copolymers containing polysiloxane sequences
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L87/00—Compositions of unspecified macromolecular compounds, obtained otherwise than by polymerisation reactions only involving unsaturated carbon-to-carbon bonds
  • C08L87/005—Block or graft polymers not provided for in groups C08L1/00 - C08L85/04

Definitions

• the invention relates to a process for modifying nanofillers, in particular unmodified clays of the montmorillonite type, and to its applications.
• lamellar silicates (phyllosilicates) are being used ever more frequently, principally because they are easy to use and widely available on the market at a reasonable price.
• the best known example of such clays is natural montmorillonite (i.e. not organomodified). Organomodified clays do not exist in the natural state and must thus be prepared by synthesis.
• Such nanofillers or organomodified clays are prepared in polar solvents such as water or alcohols such as methanol over periods of several hours and at moderately high temperatures, usually 70° C.
• polar solvents such as water or alcohols such as methanol
• a quaternary ammonium, sulphonium or phosphonium salt is brought into the presence of a natural clay having sodium ions ionically bonded to oxygen counter-ions (O ⁇ Na + ) on the surface of each sheet.
• oxygen counter-ions O ⁇ Na +
• the wet clay After the modification reaction in water or alcohol, the wet clay has to be filtered and then dried, requiring considerable energy expenditure because of the high latent heat of vaporization of the solvents used, which constitutes a major disadvantage of this “wet” method. Further, following exchange, the contaminated water has to be purified before discharge. That method of preparation in water or an alcohol also has a serious limitation as regards the restricted range of organomodifiers (of the ammonium, phosphonium type) which can be used. In fact, the success of the wet method for modifying clays is highly dependent on the original solubility of the organomodifier in the medium in which the clay is to be dispersed during modification thereof. Further, the modification of clays by highly fluorinated or siliconated organomodifiers would necessitate the use of suitable solvents which are usually not cheap, thereby further cutting the profitability of such a process.
• the present invention aims to overcome all of the limitations of the wet process by proposing a flexible, rapid and economic process for modifying clays which at no point uses a conventional solvent.
• the unmodified clay is intimately mixed with an organomodifier selected from quaternary ammonium salts, sulphonium salts, phosphonium salts, siliconated ammonium compounds, highly fluorinated ammonium compounds, quaternary ammonium compound precursors and mixtures of at least two of said compounds, in the presence of carbon dioxide under pressure, the clay and organomodifier advantageously being intimately mixed before being brought into contact with C0 2 under pressure.
• an organomodifier selected from quaternary ammonium salts, sulphonium salts, phosphonium salts, siliconated ammonium compounds, highly fluorinated ammonium compounds, quaternary ammonium compound precursors and mixtures of at least two of said compounds
• This method termed a “dry” method, is consequently based on the use of compressed carbon dioxide and preferably brought to a supercritical condition as the medium for dispersing the clay and for modification thereof. Dispersing clays in the supercritical CO 2 is relatively easy because of the low viscosity of supercritical fluids. Further, the integration of molecules into the inter-sheet space of the clay (impregnation step) profits from the high diffusivity of mixtures based on supercritical fluids. Since said impregnation step is accompanied by a negative variation in volume, the process will be favoured by operating at high pressure, such as that routinely used during processes employing supercritical or highly compressed fluids, i.e. at pressures of 50 to 300 bars and at a temperature of 40° C. to 50° C., advantageously about 40° C.
• Example 6 pertains to the preparation of organomodified clays not starting from an ammonium compound added as is, but starting from its “parent” molecules, i.e. an amine and an alkyl halide. It is in fact a process starting from the “raw” ingredients, which has the advantage of generating a clay with a higher added value.
• Unmodified clay (Cloisite® N + ; 2 to 5 g) was intimately mixed with a slight excess (1.1 equivalent) of each of the three quaternary ammonium salts indicated in Table 5 [sic] below then poured into a high pressure reactor with a volume of 100 ml. the temperature and CO 2 pressure in the chamber were then adjusted and maintained at the desired values (40° C. and 200 bars). Ion exchange was carried out with constant stirring (700 rpm) during the time period indicated in Table 1. After reaction, the reactor was slowly depressurized. In order to characterize the recovered powder, it was washed with water, with a water/methanol mixture (1/1 volume/volume) and with methanol, then finally dried.
• the mass increase was calculated by TGA and the powder was characterized by X ray diffraction.
• the use of the solvents noted above was only justified because non-exchanged ammonium has to be removed in order to provide better characterization during analyses of the clay which has been modified in supercritical CO 2 using the dry method.
• the percentage ion exchange is the ratio between the quantity of quaternary ammonium cations fixed on the surface of the clay sheets (determined by thermogravimetric analysis (TGA)) and the maximum theoretical quantity of said cations assuming complete ion exchange (determined initially from the exchange capacity of Cloisite Na + , namely 92 meq/100 g of clay). This percentage thus corresponds to the percentage of Na + ions effectively displaced by ammonium # ions during the exchange reaction.
• the interplanar spacing d 001 measures the mean distance separating two sheets of clay following modification of said clay by an alkylammonium. This distance is measured by X ray diffraction.
• the native clay or virgin clay or non-organomodified clay
• Example 2 The three experiments were carried out using the operating procedure of Example 1, i.e. at 40° C. and at a pressure of 200 bars.
• the organomodifying agent used was DDDMABr, i.e. didodecyldimethylammonium bromide.
• Example 2 The three experiments were carried out using the operating procedure of Example 1, i.e. at 40° C. and 200 bars, for 10 minutes.
• 0.84 g of DDDMABr didodecyldimethylammonium bromide was intimately mixed with 2 g of Cloisite® Na + and the mixture then underwent treatment with supercritical CO 2 .
• Example 2 The three experiments were carried out using the operating procedure of Example 1, i.e. at 40° C. and 200 bars, for one hour. Each experiment used 2 g of Cloisite® Na + .
• Table 4 clearly shows the effect of the quantity of ammonium exchanged with the clay on the interplanar spacing thereof. It is important to note that this distance is only substantially modified when the ammonium salt added is in a quantity close to the cationic exchange capacity of the virgin clay. This observation may be explained by a modification in the orientation of the alkyl chains carried by the quaternary ammonium ions during subsequent addition of ammonium salts. Initially, these chains tend to be disposed parallel to the plane of the clay sheets, inducing a slight separation of the sheets. As soon as the organic layer covers the entire surface of the sheets, the chains have to superimpose themselves to allow the incorporation of more cations.
• the position of the alkyl chains is modified and they tend to adopt an orientation which is increasingly perpendicular to the planes of the clay sheets.
• the maximum separation therebetween can thus only be obtained when almost all of the alkali ions have been displaced by ammonium ions.
• ammonium compounds used in Examples 1 to 4 are in fact hydrophilic ammonium compounds, i.e. alkylammonium salts. Such ammonium compounds may also be used during the modification of clay fillers in aqueous media, which is not the case when using hydrophobic ammonium compounds. In effect, the ammonium compounds are less soluble in the medium and are difficult to integrate into and exchange within the clay sheets. Highly fluorinated derivatives and siliconated derivatives occupy an important place among hydrophobic ammonium compounds as they open up real opportunities for the effective preparation of nanocomposites of fluorinated or siliconated polymers. Two examples will be given below of the preparation of said novel clays in supercritical CO 2 , a medium known to be a relatively good solvent for silicones and highly fluorinated derivatives.
• Example 6 0.55 g of this modified PDMS and 1 g of Cloisite®Na + were then introduced into the reactor and the procedure of Example 6 was carried out. Ion exchange was carried out at 40° C. over 3 hours and at a pressure of 100 bars of CO 2 . The interplanar spacing obtained was 16.5 ⁇ and the ion exchange percentage was 60%.
• Example 2 0.52 g of the fluorinated ammonium compound obtained and 1 g of Cloisite® Na + were introduced into the reactor and the procedure of Example 1 was followed. Ion exchange was carried out at 40° C. for 3 hours at a pressure of 100 bars of supercritical CO 2 . The interplanar spacing obtained was 13.1 ⁇ and the percentage ion exchange was 32%.
• the degree of cationic exchange was not high. This tends to demonstrate that the more soluble the organophilic cation is in supercritical CO 2 , the harder it is to incorporate it into the clay.
• this example pertains to the preparation of organomodified clays starting from a virgin clay and quaternary ammonium compound precursors, i.e. the corresponding amine and a suitable alkyl halide.
• the treatment resulting from a step for synthesis of the ammonium compound followed by its incorporation and exchange within natural clay sheets, was carried out at 40° C. for 24 hours at a pressure of 300 bars of supercritical C0 2 in the presence of 0.37 ml of bromooctane, 1.4 ml of tridodecylamine and 2 g of Cloisite® Na + .
• the operating procedure described in Example 1 was then carried out.
• the interplanar spacing obtained was 20.3 ⁇ and the degree of ion exchange was 63%.
• While the present process pertains to the modification of unmodified clays in general, it is particularly suited to the modification of montmorillonite type clays.
• the principle of this modification resides in the excellent transport properties of CO 2 , and in particular of supercritical CO 2 , allowing good impregnation of the interplanar space by the alkylammonium compounds and therefore facilitating ion exchange at the surface of the clay sheets.
• This modification of native clays in supercritical CO 2 thus renders them organophilic and far more compatible with polymer matrices, thus facilitating their dispersion and the preparation of nanocomposites with mainly exfoliated clay fillers.
• the use of (supercritical) CO 2 can also readily allow the preparation of modified clays by ammonium compounds carrying siliconated or highly fluorinated segments.

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• Organic Chemistry (AREA)
• Health & Medical Sciences (AREA)
• Polymers & Plastics (AREA)
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• Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
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• Silicates, Zeolites, And Molecular Sieves (AREA)

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• 2003
  • 2003-06-06 EP EP03076761A patent/EP1484357A1/de not_active Withdrawn
• 2004
  • 2004-04-23 EP EP04729079A patent/EP1636298A1/de not_active Withdrawn
  • 2004-04-23 WO PCT/EP2004/004389 patent/WO2004108806A1/fr not_active Ceased
  • 2004-04-23 AT AT04729099T patent/ATE525423T1/de not_active IP Right Cessation
  • 2004-04-23 EP EP04729099A patent/EP1636299B1/de not_active Expired - Lifetime
  • 2004-04-23 US US10/559,832 patent/US20060140842A1/en not_active Abandoned
  • 2004-04-23 WO PCT/EP2004/004388 patent/WO2004108805A1/fr not_active Ceased

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